CN108975918A - A kind of high tenacity high-temperature structural material MoSi2-Mo5Si3The preparation of composite ceramics - Google Patents

Abstract

The invention discloses a kind of high tenacity high-temperature structural material MoSi₂‑Mo₅Si₃The preparation method of composite ceramics.A kind of thermal structure composite ceramic material with high tenacity is related generally to, high-temperature structural ceramics field is belonged to.Molybdenum disilicide and three silication, five molybdenum powder are mixed according to a certain percentage after high-energy ball milling, vacuum processing and high-melting-point lapping encapsulate precompressed, sinter the composite ceramics of high tenacity under conditions of 3 ~ 15GPa, 700 ~ 1800 DEG C.The present invention has prepared the MoSi with high tenacity using high temperature and high pressure method for the first time₂‑Mo₅Si₃The characteristics of composite ceramic material, small with crystallite dimension, crystallinity is high, consistency height, stable structure.Because of its preparation process simply and with having very big application potential under extreme conditions, it can be used as high temperature exothermic element and high-temperature oxidation resistant coating material, can also be used as the candidate material of aircraft, rocket engine high temperature resistant component.

Description

Preparation of MoSi2-Mo5Si3 Composite Ceramics with High Toughness and High Temperature Structure

technical field

The invention relates to a high-toughness high-temperature structural material MoSi ₂ -Mo ₅ Si ₃ composite ceramics, in particular to a high-toughness high-temperature structural material MoSi ₂ -Mo ₅ Si ₃ ceramics and a preparation method thereof, belonging to the field of high-temperature structural ceramic materials.

Background technique

MoSi ₂ has a high melting point (2030 ℃), moderate density (6.24 g/cm ³ ), excellent high-temperature oxidation resistance, and good thermal and electrical conductivity. It is an important material for manufacturing high-temperature heating elements It is the third-generation ultra-high-temperature structural material after the Ni-based superalloy and the second-generation superalloy TiAl. It has a high melting point, low density and excellent high-temperature oxidation resistance. However, due to its large low-temperature brittleness, insufficient high-temperature strength, especially creep strength, and poor oxidation resistance at 400-600 °C, its industrial application is limited. Its performance can be enhanced through multi-phase synergistic preparation, and multi-phase synergy helps to improve the comprehensive mechanical properties of materials. It is believed that alloying synergistically with the second phase compounding, compounding and alloying "a small amount of multi-component" is the future to improve MoSi ₂ high temperature The important development direction of the comprehensive properties of structural materials can be improved by adding Mo ₅ Si ₃ phase to prepare MoSi ₂ -Mo ₅ Si ₃ composite ceramics. However, the application of MoSi ₂ -Mo ₅ Si ₃ composite ceramics is limited due to the difficulty of sintering, low toughness and difficulty in densification. Conventional methods for preparing composite ceramics include:

Mechanical alloying (N. Iwatomo, et al., J. Amer. Chem. Soc. 1990, 177-180), which is a technique of high-energy ball milling of powders to synthesize materials. This method mainly relies on high-energy ball milling. Although the crystal grains can be refined, it is easy to introduce impurities and reduce the performance of the sample.

Self-propagating high-temperature synthesis (C.C. Deevi, Mater. Sci. Eng. A, 1992, 149, 241-251), this method is a technology that uses the strong exothermic reaction between powder elements to form new materials. This method is difficult to obtain dense materials, and it is difficult to control the synthesis reaction process and material properties due to the high reaction speed.

Hot isostatic pressing method (S.M..L. Sdstry, et al., Mater. Sci. Eng. A, 1995, 192/193, 880-890), the preparation of this method is easy to grow grains, requires high temperature conditions, and costs High, complex process, difficult to obtain high toughness materials.

Solid-state displacement reaction (C.H. Henger, et al., Mater. Sci. Eng. A, 1997, 225, 105-117), which is a technique for preparing intermetallic compound-based composite materials. The solid-state displacement reaction can produce very clean matrix-reinforcement interface without external contamination. However, solid-state displacement reactions controlled by diffusion are usually slow and energy-intensive, which limits their applications.

In situ reaction hot pressing, this method is a very effective synthesis method for high melting point silicides and other intermetallic compounds that are not easily sintered. This method eliminates the incompatibility of the interface between the matrix phase and the reinforcing phase, ensures the thermodynamic stability of the matrix phase and the reinforcing phase, and makes the interface clean, with a controllable structure and good combination. The reaction time is long, the required temperature is high, and it is difficult to Obtain samples with high toughness and high density.

Plasma spray deposition method (R. Tiwari, et al., Mater. Sci. Eng. A, 1992, 155, 95), which is a near-static forming manufacturing method, which melts, mixes and consolidates in completed in one process. This method can obtain fine crystal grains and uniform microstructure, which is conducive to improving the mechanical properties of the product. Obtaining fine grains and uniform microstructure is beneficial to improving the mechanical properties of the product, but the toughness of the and the increase in density is very limited.

It is difficult to prepare MoSi ₂ -Mo ₅ Si ₃ composite ceramic materials with high fracture toughness and high density by the above-mentioned conventional methods, and the preparation of MoSi ₂ -Mo ₅ Si ₃ composite ceramic bulk materials with high toughness and high density has always been a huge challenge. challenge. MoSi ₂ -based composites are widely used in extreme conditions due to their excellent physical and chemical properties. In order to obtain the MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body, we used the domestic hinged six-sided top press and directly used the multi-phase sintering method under high temperature and high pressure conditions to prepare a large sintered body with excellent performance and application value. The preparation process of the invention is simple, beneficial to industrial production, and has the characteristics of high toughness, high density, high melting point, high hardness, and high oxidation resistance, and can be used as a high-temperature heating element and high-temperature oxidation-resistant coating material, and can also As a candidate material for high temperature resistant components of aircraft and rocket engines, it has great application potential under extreme conditions.

Contents of the invention

The purpose of the present invention is to overcome the shortcomings and deficiencies of the traditional preparation method, and provide a high-toughness high-temperature structural material MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body and a preparation method thereof. The problems of low toughness, poor hardness and difficulty in densification of samples prepared by traditional preparation methods have been solved. In the present invention, molybdenum disilicide and pentamolybdenum trisilicide are used as initial raw materials, mixed according to the mass ratio of 19:1 to 7:3, and directly sintered under the conditions of 3 to 15 GPa, 700 to 1800 ° C, and a holding time of 5 to 100 minutes. MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body. The high-density hafnium diboride ceramics provided by the invention have remarkable characteristics such as high fracture toughness, high density, high hardness, small grain size and excellent oxidation resistance. The high-toughness ultra-high-temperature structural material MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body provided by the present invention has a fracture toughness of 10.7 Mpa m ^1/2 and a Vickers hardness of 15.0 GPa, (the preparation conditions are 5.5 GPa, 1300 °C, heat preservation 20 minutes; the hardness measurement condition is 15 s under the loading force of 3 Kgf), the density is as high as 99.7%, and the oxidation resistance is higher than 1400 ℃

The high-toughness high-temperature structural material MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body method provided by the present invention comprises the following steps:

Step 1: Mix molybdenum disilicide with hexagonal structure and pentamolybdenum trisilicide powder with hexagonal structure according to a certain ratio;

The second step: high-energy ball milling the mixed disilicide and pentamolybdenum trisilicide powder;

The third step: Pickling the mixed powder of disilicide and pentamolybdenum trisilicide after ball milling;

Step 4: Carry out high-temperature vacuum treatment on the mixed powder of disilicide and trisilicide pentamolybdenum after pickling, encapsulate it with high melting point wrapping material, and pre-press it into a cylinder;

Step 5: Put the pre-pressed cylinder into the high-pressure synthesis assembly, and place the assembled high-pressure synthesis assembly in the synthesis cavity for high-temperature and high-pressure sintering;

Step 6: After the sintering is completed, reduce the temperature and release the pressure to remove the inclusions, take out the sintered block, and then pickle to remove the inclusions, and then the high-toughness and high-temperature structural material MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body can be obtained.

In the first step of the method of the present invention, the disilicide and trisilicide pentamolybdenum powders are preferably hexagonal, and the particle size is 0.1-10 μm. The mixed powders are sintered directly under high temperature and high pressure to form a high-toughness high-temperature structural material MoSi ₂ -Mo ₅ Si ₃ composite ceramic bulk material. In the first step of the method, molybdenum disilicide with hexagonal structure and pentamolybdenum trisilicide with hexagonal structure are mixed according to the mass ratio (19:1)-(7:3).

In the second step of the method, the high-energy ball mill uses normal hexane, ethanol or stearic acid, etc. as the high-energy ball mill process control agent, and uses high-speed steel balls, zirconia balls or agate balls as high-energy balls, and the high-energy ball mill ball-to-material ratio is 10: 1,9:1 or 8:1, the ball milling speed is 250~500 r/min and the ball milling time is 5~50 hours.

In the third step of the method of the present invention, pickling is carried out with aqua regia or concentrated hydrochloric acid or concentrated sulfuric acid to remove impurities introduced during the high-energy ball milling process.

The conditions for the high-temperature vacuum treatment in the fourth step of the method of the present invention are: temperature 500-1500 °C, vacuum degree 1 Pa-1×10 ^-5 Pa, heat preservation for 10-120 minutes. The purpose of the vacuum treatment is to remove the adsorbed impurities in the raw material as well as the organic solvent introduced in the second step of the process. The high-melting-point wrapping material used for packaging in the fourth step of the method can be made of high-temperature-resistant metals such as molybdenum, tantalum, niobium, platinum, and gold.

The package cylinder pre-pressed in the fifth step of the method of the present invention is placed in the salt tube in the pyrophyllite synthetic block, the upper and lower ends of the salt tube are sealed with salt flakes to form a salt column, and then the salt column is put into the graphite tube, The upper and lower ends of the graphite tube are sequentially assembled with graphite sheets to form a graphite column. The graphite column is placed in the dolomite tube, and the dolomite sheet, molybdenum sheet and conductive steel ring with the graphite column in the middle are assembled at the two ends of the dolomite tube. After being assembled in the fifth step of the method, the synthetic block is put into the synthetic chamber of a large press, and the high temperature and high pressure conditions are preferably selected with a pressure of 3 to 15 GPa, a temperature of about 700 to 1800 °C, and heat preservation and pressure for 5 to 100 minutes. The suitable equipment for the high-temperature and high-pressure synthesis process in the fifth step of the method may be double-sided presses, four-sided presses, six-sided presses and equipment capable of generating high-temperature and high-pressure conditions.

In the sixth step of the method of the present invention, the acid for washing out the high melting point metal is aqua regia, concentrated hydrochloric acid or concentrated sulfuric acid.

Beneficial effect

(1) The present invention uses molybdenum disilicide with hexagonal structure and pentamolybdenum trisilicide powder with hexagonal structure as initial raw materials, and provides a MoSi ₂ -Mo ₅ Si ₃ composite ceramic with high toughness directly sintered under high temperature and high pressure conditions Methods for bulk materials. It has the characteristics of low cost, environmental friendliness, simple sintering process, good product performance and high yield.

(2) The samples prepared by the present invention are tested by micro-indentation, and the sintered body has high fracture toughness and high hardness. The sample prepared by the invention is analyzed by XRD and scanning electron microscope, and the average grain size of the sintered body is less than 3 μm, and there are a large number of nanostructure grains at the same time, with low porosity and high density. The samples prepared by the invention are subjected to thermogravimetric analysis, and the sintered body has excellent oxidation resistance. The invention can be sintered under relatively low temperature and pressure conditions (minimum synthesis conditions are 700 °C temperature and 3 GPa pressure), and has the advantages of easy popularization and large-scale production.

(3) The high toughness MoSi ₂ -Mo ₅ Si ₃ composite ceramic block is obtained by adopting the method provided by the present invention, which has the remarkable characteristics of high fracture toughness, high density, high hardness, and high density.

Description of drawings

Fig. 1 is a physical photo of the high-toughness high-temperature structural material MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body prepared by the present invention.

Fig. 2 is the XRD spectrum of the high toughness high temperature structural material MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body prepared by the present invention (Example 13).

Fig. 3 is a scanning electron microscope image of the high-toughness high-temperature structural material MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body prepared by the present invention (Example 13).

Detailed ways

Embodiment 1: Take molybdenum disilicide with hexagonal structure and pentamolybdenum trisilicide powder with hexagonal structure with a mass ratio of 19:1 as initial raw materials, carry out high-energy ball milling and pickling treatment on the selected raw materials, and place the processed powder at high temperature Carry out vacuum treatment at 600 °C in a vacuum furnace with a vacuum degree of 1 Pa and a holding time of 120 minutes, then put it into a high-melting point wrapping material for packaging and pre-press under a pressure of 600 MPa to obtain a cylindrical inclusion, and then put pyrophyllite In the salt tube in the synthesis block, the upper and lower ends of the salt tube are sealed with salt sheets to form a salt column, and then the salt column is put into the graphite tube, and the upper and lower ends of the graphite tube are assembled with graphite sheets in turn to form an ink column, and then the graphite column Placed in a dolomite tube, the two ends of the dolomite tube are assembled with a dolomite sheet with a graphite column in the middle, a molybdenum sheet and a conductive steel ring. Molybdenum sheet and conductive steel ring. Put the synthetic block into the synthetic cavity of the large press after assembling, press at a temperature of 700 ℃, press about 3 GPa, keep the heat for 20 minutes, take out the material after cooling down and releasing the pressure, soak in aqua regia, and remove the metal inclusions Afterwards, a MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body is obtained.

Embodiment 2: Take molybdenum disilicide with hexagonal structure and pentamolybdenum trisilicide powder with hexagonal structure with a mass ratio of 19:1 as initial raw materials, carry out high-energy ball milling and pickling treatment on the selected raw materials, and place the processed powder at high temperature Carry out vacuum treatment at 600 °C in a vacuum furnace with a vacuum degree of 1 Pa and a holding time of 120 minutes, then put it into a high-melting point wrapping material for packaging and pre-press under a pressure of 600 MPa to obtain a cylindrical inclusion, and then put pyrophyllite In the salt tube in the synthesis block, the upper and lower ends of the salt tube are sealed with salt sheets to form a salt column, and then the salt column is put into the graphite tube, and the upper and lower ends of the graphite tube are assembled with graphite sheets in turn to form an ink column, and then the graphite column Placed in a dolomite tube, the two ends of the dolomite tube are assembled with a dolomite sheet with a graphite column in the middle, a molybdenum sheet and a conductive steel ring. Molybdenum sheet and conductive steel ring. After assembling, put the synthetic block into the synthetic cavity of the large press, press at a temperature of 900 ℃, press about 5.5 GPa, hold the heat for 10 minutes, take out the material after cooling down and releasing the pressure, soak in aqua regia, and remove the metal inclusions Afterwards, a MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body is obtained.

Embodiment 3: Take molybdenum disilicide of hexagonal structure and pentamolybdenum trisilicide powder of hexagonal structure with a mass ratio of 19:1 as initial raw materials, carry out high-energy ball milling and pickling treatment on the selected raw materials, and place the processed powder at high temperature Carry out vacuum treatment at 600 °C in a vacuum furnace with a vacuum degree of 1 Pa and a holding time of 120 minutes, then put it into a high-melting point wrapping material for packaging and pre-press under a pressure of 600 MPa to obtain a cylindrical inclusion, and then put pyrophyllite In the salt tube in the synthesis block, the upper and lower ends of the salt tube are sealed with salt sheets to form a salt column, and then the salt column is put into the graphite tube, and the upper and lower ends of the graphite tube are assembled with graphite sheets in turn to form an ink column, and then the graphite column Placed in a dolomite tube, the two ends of the dolomite tube are assembled with a dolomite sheet with a graphite column in the middle, a molybdenum sheet and a conductive steel ring. Molybdenum sheet and conductive steel ring. After assembling, put the synthetic block into the synthetic cavity of the large press, press at about 8 GPa at a temperature of 800 ℃, keep the heat for 5 minutes, take out the material after cooling down and releasing the pressure, soak in aqua regia, and remove the metal inclusions Afterwards, a MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body is obtained.

Embodiment 4: Take molybdenum disilicide of hexagonal structure and pentamolybdenum trisilicide powder of hexagonal structure with a mass ratio of 19:1 as initial raw materials, carry out high-energy ball milling and pickling treatment on the selected raw materials, and place the processed powder at high temperature Carry out vacuum treatment at 600 °C in a vacuum furnace with a vacuum degree of 1 Pa and a holding time of 120 minutes, then put it into a high-melting point wrapping material for packaging and pre-press under a pressure of 600 MPa to obtain a cylindrical inclusion, and then put pyrophyllite In the salt tube in the synthesis block, the upper and lower ends of the salt tube are sealed with salt sheets to form a salt column, and then the salt column is put into the graphite tube, and the upper and lower ends of the graphite tube are assembled with graphite sheets in turn to form an ink column, and then the graphite column Placed in a dolomite tube, the two ends of the dolomite tube are assembled with a dolomite sheet with a graphite column in the middle, a molybdenum sheet and a conductive steel ring. Molybdenum sheet and conductive steel ring. After assembling, put the synthetic block into the synthetic chamber of the large press, press at a temperature of 1000 ℃, press about 9 GPa, hold the heat for 30 minutes, take out the material after cooling down and releasing the pressure, soak in aqua regia, and remove the metal inclusions Afterwards, a MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body is obtained.

Embodiment 5: Take molybdenum disilicide of hexagonal structure and pentamolybdenum trisilicide powder of hexagonal structure with a mass ratio of 19:1 as initial raw materials, carry out high-energy ball milling and pickling treatment on the selected raw materials, and place the processed powder at high temperature Carry out vacuum treatment at 600 °C in a vacuum furnace with a vacuum degree of 1 Pa and a holding time of 120 minutes, then put it into a high-melting point wrapping material for packaging and pre-press under a pressure of 600 MPa to obtain a cylindrical inclusion, and then put pyrophyllite In the salt tube in the synthesis block, the upper and lower ends of the salt tube are sealed with salt sheets to form a salt column, and then the salt column is put into the graphite tube, and the upper and lower ends of the graphite tube are assembled with graphite sheets in turn to form an ink column, and then the graphite column Placed in a dolomite tube, the two ends of the dolomite tube are assembled with a dolomite sheet with a graphite column in the middle, a molybdenum sheet and a conductive steel ring. Molybdenum sheet and conductive steel ring. After assembly, put the synthetic block into the synthetic chamber of the large press, press at a temperature of 1100 ℃, press about 10 GPa, hold the heat for 40 minutes, take out the material after cooling down and releasing the pressure, soak in aqua regia, and remove the metal inclusions Afterwards, a MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body is obtained.

Embodiment 6: Take molybdenum disilicide with hexagonal structure and pentamolybdenum trisilicide powder with hexagonal structure with a mass ratio of 19:1 as initial raw materials, carry out high-energy ball milling and pickling treatment on the selected raw materials, and place the processed powder at high temperature Carry out vacuum treatment at 600 °C in a vacuum furnace with a vacuum degree of 1 Pa and a holding time of 120 minutes, then put it into a high-melting point wrapping material for packaging and pre-press under a pressure of 600 MPa to obtain a cylindrical inclusion, and then put pyrophyllite In the salt tube in the synthesis block, the upper and lower ends of the salt tube are sealed with salt sheets to form a salt column, and then the salt column is put into the graphite tube, and the upper and lower ends of the graphite tube are assembled with graphite sheets in turn to form an ink column, and then the graphite column Placed in a dolomite tube, the two ends of the dolomite tube are assembled with a dolomite sheet with a graphite column in the middle, a molybdenum sheet and a conductive steel ring. Molybdenum sheet and conductive steel ring. After assembly, put the synthetic block into the synthetic chamber of the large press, press at a temperature of 1300 ℃, press about 11 GPa, keep the heat for 15 minutes, take out the material after cooling down and releasing the pressure, soak in aqua regia, and remove the metal inclusions Afterwards, a MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body is obtained.

Embodiment 7: Take hexagonal molybdenum disilicide and hexagonal molybdenum trisilicide pentamolybdenum powders with a mass ratio of 19:1 as initial raw materials, carry out high-energy ball milling and pickling treatment on the selected raw materials, and place the processed powders at high temperature Carry out vacuum treatment at 600 °C in a vacuum furnace with a vacuum degree of 1 Pa and a holding time of 120 minutes, then put it into a high-melting point wrapping material for packaging and pre-press under a pressure of 600 MPa to obtain a cylindrical inclusion, and then put pyrophyllite In the salt tube in the synthesis block, the upper and lower ends of the salt tube are sealed with salt sheets to form a salt column, and then the salt column is put into the graphite tube, and the upper and lower ends of the graphite tube are assembled with graphite sheets in turn to form an ink column, and then the graphite column Placed in a dolomite tube, the two ends of the dolomite tube are assembled with a dolomite sheet with a graphite column in the middle, a molybdenum sheet and a conductive steel ring. Molybdenum sheet and conductive steel ring. Put the synthetic block into the synthetic cavity of the large press after assembling, press at a temperature of 1400 ℃, press about 12 GPa, hold the heat for 60 minutes, take out the material after cooling down and releasing the pressure, soak in aqua regia, and remove the metal inclusions Afterwards, a MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body is obtained.

Embodiment 8: Take molybdenum disilicide with hexagonal structure and pentamolybdenum trisilicide powder with hexagonal structure with a mass ratio of 19:1 as initial raw materials, carry out high-energy ball milling and pickling treatment on the selected raw materials, and place the processed powder at high temperature Carry out vacuum treatment at 600 °C in a vacuum furnace with a vacuum degree of 1 Pa and a holding time of 120 minutes, then put it into a high-melting point wrapping material for packaging and pre-press under a pressure of 600 MPa to obtain a cylindrical inclusion, and then put pyrophyllite In the salt tube in the synthesis block, the upper and lower ends of the salt tube are sealed with salt sheets to form a salt column, and then the salt column is put into the graphite tube, and the upper and lower ends of the graphite tube are assembled with graphite sheets in turn to form an ink column, and then the graphite column Placed in a dolomite tube, the two ends of the dolomite tube are assembled with a dolomite sheet with a graphite column in the middle, a molybdenum sheet and a conductive steel ring. Molybdenum sheet and conductive steel ring. After assembling, put the synthetic block into the synthetic chamber of the large press, press at a temperature of 1200 ℃, press about 13 GPa, hold the heat for 100 minutes, take out the material after cooling down and releasing the pressure, soak in aqua regia, and remove the metal inclusions Afterwards, a MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body is obtained.

Embodiment 9: Take molybdenum disilicide with hexagonal structure and pentamolybdenum trisilicide powder with hexagonal structure at a mass ratio of 19:1 as initial raw materials, carry out high-energy ball milling and pickling treatment on the selected raw materials, and place the processed powder at high temperature Carry out vacuum treatment at 600 °C in a vacuum furnace with a vacuum degree of 1 Pa and a holding time of 120 minutes, then put it into a high-melting point wrapping material for packaging and pre-press under a pressure of 600 MPa to obtain a cylindrical inclusion, and then put pyrophyllite In the salt tube in the synthesis block, the upper and lower ends of the salt tube are sealed with salt sheets to form a salt column, and then the salt column is put into the graphite tube, and the upper and lower ends of the graphite tube are assembled with graphite sheets in turn to form an ink column, and then the graphite column Placed in a dolomite tube, the two ends of the dolomite tube are assembled with a dolomite sheet with a graphite column in the middle, a molybdenum sheet and a conductive steel ring. Molybdenum sheet and conductive steel ring. After assembling, put the synthetic block into the synthetic cavity of the large press, press at about 14 GPa at a temperature of 1600 ℃, keep the heat for 40 minutes, take out the material after cooling down and releasing the pressure, soak in aqua regia, and remove the metal inclusions Afterwards, a MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body is obtained.

Embodiment 10: Take hexagonal molybdenum disilicide and hexagonal molybdenum trisilicide pentamolybdenum powders with a mass ratio of 19:1 as initial raw materials, carry out high-energy ball milling and pickling treatment on the selected raw materials, and place the processed powders at high temperature Carry out vacuum treatment at 600 °C in a vacuum furnace with a vacuum degree of 1 Pa and a holding time of 120 minutes, then put it into a high-melting point wrapping material for packaging and pre-press under a pressure of 600 MPa to obtain a cylindrical inclusion, and then put pyrophyllite In the salt tube in the synthesis block, the upper and lower ends of the salt tube are sealed with salt sheets to form a salt column, and then the salt column is put into the graphite tube, and the upper and lower ends of the graphite tube are assembled with graphite sheets in turn to form an ink column, and then the graphite column Placed in a dolomite tube, the two ends of the dolomite tube are assembled with a dolomite sheet with a graphite column in the middle, a molybdenum sheet and a conductive steel ring. Molybdenum sheet and conductive steel ring. After assembling, put the synthetic block into the synthetic cavity of the large press, press at a temperature of 1800 ℃, press about 15 GPa, hold the heat for 10 minutes, take out the material after cooling down and releasing the pressure, soak in aqua regia, and remove the metal inclusions Afterwards, a MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body is obtained.

Embodiment 11: Take molybdenum disilicide with hexagonal structure and pentamolybdenum trisilicide powder with hexagonal structure with a mass ratio of 9:1 as initial raw materials, carry out high-energy ball milling and pickling treatment on the selected raw materials, and place the processed powder in Carry out vacuum treatment at 600 ℃ in a high-temperature vacuum furnace, the vacuum degree is 1 Pa, and the holding time is 120 minutes. In the salt tube in the pyrophyllite synthesis block, the upper and lower ends of the salt tube are sealed with salt sheets to form a salt column, and then the salt column is put into the graphite tube, and the upper and lower ends of the graphite tube are sequentially assembled with graphite sheets to form an ink column, and then the graphite The column is placed in a dolomite tube, and the two ends of the dolomite tube are assembled with a dolomite sheet with a graphite column in the middle, a molybdenum sheet and a conductive steel ring. Molybdenum sheet and conductive steel ring. After assembling, put the synthetic block into the synthetic chamber of the large press, press at a temperature of 800 ℃, press about 3 GPa, hold the heat for 5 minutes, take out the material after cooling down and releasing the pressure, soak in aqua regia, and remove the metal inclusions Afterwards, a MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body is obtained.

Embodiment 12: Take molybdenum disilicide with hexagonal structure and pentamolybdenum trisilicide powder with hexagonal structure with a mass ratio of 9:1 as initial raw materials, carry out high-energy ball milling and pickling treatment on the selected raw materials, and place the processed powder in Carry out vacuum treatment at 600 ℃ in a high-temperature vacuum furnace, the vacuum degree is 1 Pa, and the holding time is 120 minutes. In the salt tube in the pyrophyllite synthesis block, the upper and lower ends of the salt tube are sealed with salt sheets to form a salt column, and then the salt column is put into the graphite tube, and the upper and lower ends of the graphite tube are sequentially assembled with graphite sheets to form an ink column, and then the graphite The column is placed in a dolomite tube, and the two ends of the dolomite tube are assembled with a dolomite sheet with a graphite column in the middle, a molybdenum sheet and a conductive steel ring. Molybdenum sheet and conductive steel ring. After assembling, put the synthetic block into the synthetic chamber of the large press, press at a temperature of 900 ℃, press about 4 GPa, hold the heat for 60 minutes, take out the material after cooling down and releasing the pressure, soak in aqua regia, and remove the metal inclusions Afterwards, a MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body is obtained.

Embodiment 13: Take molybdenum disilicide with hexagonal structure and pentamolybdenum trisilicide powder with hexagonal structure with a mass ratio of 9:1 as initial raw materials, carry out high-energy ball milling and pickling treatment on the selected raw materials, and place the processed powder in Carry out vacuum treatment at 600 ℃ in a high-temperature vacuum furnace, the vacuum degree is 1 Pa, and the holding time is 120 minutes. In the salt tube in the pyrophyllite synthesis block, the upper and lower ends of the salt tube are sealed with salt sheets to form a salt column, and then the salt column is put into the graphite tube, and the upper and lower ends of the graphite tube are sequentially assembled with graphite sheets to form an ink column, and then the graphite The column is placed in a dolomite tube, and the two ends of the dolomite tube are assembled with a dolomite sheet with a graphite column in the middle, a molybdenum sheet and a conductive steel ring. Molybdenum sheet and conductive steel ring. After assembly, put the synthetic block into the synthetic chamber of the large press, press at a temperature of 1300 ℃, press about 5.5 GPa, keep the heat for 20 minutes, take out the material after cooling down and releasing the pressure, soak in aqua regia, and remove the metal inclusions Afterwards, a MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body is obtained.

Embodiment 14: Take molybdenum disilicide with hexagonal structure and pentamolybdenum trisilicide powder with hexagonal structure with a mass ratio of 9:1 as initial raw materials, carry out high-energy ball milling and pickling treatment on the selected raw materials, and place the processed powder in Carry out vacuum treatment at 600 ℃ in a high-temperature vacuum furnace, the vacuum degree is 1 Pa, and the holding time is 120 minutes. In the salt tube in the pyrophyllite synthesis block, the upper and lower ends of the salt tube are sealed with salt sheets to form a salt column, and then the salt column is put into the graphite tube, and the upper and lower ends of the graphite tube are sequentially assembled with graphite sheets to form an ink column, and then the graphite The column is placed in a dolomite tube, and the two ends of the dolomite tube are assembled with a dolomite sheet with a graphite column in the middle, a molybdenum sheet and a conductive steel ring. Molybdenum sheet and conductive steel ring. After assembly, put the synthetic block into the synthetic chamber of the large press, press at a temperature of 700 ℃, press about 8 GPa, hold the heat for 90 minutes, take out the material after cooling down and releasing the pressure, soak in aqua regia, and remove the metal inclusions Afterwards, a MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body is obtained.

Embodiment 15: Take molybdenum disilicide with hexagonal structure and pentamolybdenum trisilicide powder with hexagonal structure with a mass ratio of 9:1 as initial raw materials, carry out high-energy ball milling and pickling treatment on the selected raw materials, and place the processed powder in Carry out vacuum treatment at 600 ℃ in a high-temperature vacuum furnace, the vacuum degree is 1 Pa, and the holding time is 120 minutes. In the salt tube in the pyrophyllite synthesis block, the upper and lower ends of the salt tube are sealed with salt sheets to form a salt column, and then the salt column is put into the graphite tube, and the upper and lower ends of the graphite tube are sequentially assembled with graphite sheets to form an ink column, and then the graphite The column is placed in a dolomite tube, and the two ends of the dolomite tube are assembled with a dolomite sheet with a graphite column in the middle, a molybdenum sheet and a conductive steel ring. Molybdenum sheet and conductive steel ring. After assembly, put the synthetic block into the synthetic chamber of the large press, press at a temperature of 1200 ℃, press about 10 GPa, hold the heat for 30 minutes, take out the material after cooling down and releasing the pressure, soak in aqua regia, and remove the metal inclusions Afterwards, a MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body is obtained.

Embodiment 16: Take molybdenum disilicide with hexagonal structure and pentamolybdenum trisilicide powder with hexagonal structure with a mass ratio of 9:1 as initial raw materials, carry out high-energy ball milling and pickling treatment on the selected raw materials, and place the processed powder in Carry out vacuum treatment at 600 ℃ in a high-temperature vacuum furnace, the vacuum degree is 1 Pa, and the holding time is 120 minutes. In the salt tube in the pyrophyllite synthesis block, the upper and lower ends of the salt tube are sealed with salt sheets to form a salt column, and then the salt column is put into the graphite tube, and the upper and lower ends of the graphite tube are sequentially assembled with graphite sheets to form an ink column, and then the graphite The column is placed in a dolomite tube, and the two ends of the dolomite tube are assembled with a dolomite sheet with a graphite column in the middle, a molybdenum sheet and a conductive steel ring. Molybdenum sheet and conductive steel ring. After assembling, put the synthetic block into the synthetic cavity of the large press, press at a temperature of 1000 ℃, press about 11 GPa, hold the heat for 40 minutes, take out the material after cooling down and releasing the pressure, soak in aqua regia, and remove the metal inclusions Afterwards, a MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body is obtained.

Embodiment 17: Take molybdenum disilicide with hexagonal structure and pentamolybdenum trisilicide powder with hexagonal structure with a mass ratio of 9:1 as initial raw materials, carry out high-energy ball milling and pickling treatment on the selected raw materials, and place the processed powder in Carry out vacuum treatment at 600 ℃ in a high-temperature vacuum furnace, the vacuum degree is 1 Pa, and the holding time is 120 minutes. In the salt tube in the pyrophyllite synthesis block, the upper and lower ends of the salt tube are sealed with salt sheets to form a salt column, and then the salt column is put into the graphite tube, and the upper and lower ends of the graphite tube are sequentially assembled with graphite sheets to form an ink column, and then the graphite The column is placed in a dolomite tube, and the two ends of the dolomite tube are assembled with a dolomite sheet with a graphite column in the middle, a molybdenum sheet and a conductive steel ring. Molybdenum sheet and conductive steel ring. After assembly, put the synthetic block into the synthetic chamber of the large press, press at a temperature of 1400 ℃, press about 12 GPa, keep the heat for 30 minutes, take out the material after cooling down and releasing the pressure, soak in aqua regia, and remove the metal inclusions Afterwards, a MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body is obtained.

Embodiment 18: Take molybdenum disilicide with hexagonal structure and pentamolybdenum trisilicide powder with hexagonal structure with a mass ratio of 9:1 as initial raw materials, carry out high-energy ball milling and pickling treatment on the selected raw materials, and place the processed powder in Carry out vacuum treatment at 600 ℃ in a high-temperature vacuum furnace, the vacuum degree is 1 Pa, and the holding time is 120 minutes. In the salt tube in the pyrophyllite synthesis block, the upper and lower ends of the salt tube are sealed with salt sheets to form a salt column, and then the salt column is put into the graphite tube, and the upper and lower ends of the graphite tube are sequentially assembled with graphite sheets to form an ink column, and then the graphite The column is placed in a dolomite tube, and the two ends of the dolomite tube are assembled with a dolomite sheet with a graphite column in the middle, a molybdenum sheet and a conductive steel ring. Molybdenum sheet and conductive steel ring. After assembling, put the synthetic block into the synthetic cavity of the large press, press at a temperature of 1800 ℃, press about 13 GPa, hold the heat for 10 minutes, take out the material after cooling down and releasing the pressure, soak in aqua regia, and remove the metal inclusions Afterwards, a MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body is obtained.

Embodiment 19: Take molybdenum disilicide with hexagonal structure and pentamolybdenum trisilicide powder with hexagonal structure with a mass ratio of 9:1 as initial raw materials, carry out high-energy ball milling and pickling treatment on the selected raw materials, and place the processed powder in Carry out vacuum treatment at 600 ℃ in a high-temperature vacuum furnace, the vacuum degree is 1 Pa, and the holding time is 120 minutes. In the salt tube in the pyrophyllite synthesis block, the upper and lower ends of the salt tube are sealed with salt sheets to form a salt column, and then the salt column is put into the graphite tube, and the upper and lower ends of the graphite tube are sequentially assembled with graphite sheets to form an ink column, and then the graphite The column is placed in a dolomite tube, and the two ends of the dolomite tube are assembled with a dolomite sheet with a graphite column in the middle, a molybdenum sheet and a conductive steel ring. Molybdenum sheet and conductive steel ring. After assembly, put the synthetic block into the synthetic chamber of the large press, press at a temperature of 1500 ℃, press about 14 GPa, keep the heat for 40 minutes, take out the material after cooling down and releasing the pressure, soak in aqua regia, and remove the metal inclusions Afterwards, a MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body is obtained.

Example 20: Take hexagonal molybdenum disilicide and hexagonal molybdenum trisilicide pentamolybdenum powders with a mass ratio of 9:1 as initial raw materials, carry out high-energy ball milling and pickling treatment on the selected raw materials, and place the processed powders in Carry out vacuum treatment at 600 ℃ in a high-temperature vacuum furnace, the vacuum degree is 1 Pa, and the holding time is 120 minutes. In the salt tube in the pyrophyllite synthesis block, the upper and lower ends of the salt tube are sealed with salt sheets to form a salt column, and then the salt column is put into the graphite tube, and the upper and lower ends of the graphite tube are sequentially assembled with graphite sheets to form an ink column, and then the graphite The column is placed in a dolomite tube, and the two ends of the dolomite tube are assembled with a dolomite sheet with a graphite column in the middle, a molybdenum sheet and a conductive steel ring. Molybdenum sheet and conductive steel ring. After assembly, put the synthetic block into the synthetic chamber of the large press, press at a temperature of 1700 ℃, press about 15 GPa, hold the heat for 20 minutes, take out the material after cooling down and releasing the pressure, soak in aqua regia, and remove the metal inclusions Afterwards, a MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body is obtained.

Example 21: Taking hexagonal molybdenum disilicide and hexagonal molybdenum trisilicide pentamolybdenum powders with a mass ratio of 19:3 as initial raw materials, the selected raw materials were subjected to high-energy ball milling and pickling treatment, and the processed powders were placed in Carry out vacuum treatment at 600 °C in a high-temperature vacuum furnace with a vacuum degree of 1 Pa and a holding time of 120 minutes, then put it into a high-melting point packaging material for packaging and pre-press under a pressure of 600 MPa to obtain a cylindrical inclusion, and then put Put into the salt tube in the pyrophyllite synthesis block, the upper and lower ends of the salt tube are sealed with salt sheets to form a salt column, and then the salt column is put into the graphite tube, and the upper and lower ends of the graphite tube are assembled with graphite sheets in turn to form an ink column, and then the The graphite column is placed in the dolomite tube, and the two ends of the dolomite tube are assembled with dolomite sheet, molybdenum sheet and conductive steel ring with graphite column in the middle. Molybdenum sheet and conductive steel ring. Put the synthetic block into the synthetic cavity of the large press after assembly, press at a temperature of 800 ℃, press about 3 GPa, keep the heat for 100 minutes, take out the material after cooling down and releasing the pressure, soak in aqua regia, and remove the metal inclusions Afterwards, a MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body is obtained.

Example 22: Taking hexagonal molybdenum disilicide and hexagonal molybdenum trisilicide pentamolybdenum powders with a mass ratio of 19:3 as initial raw materials, the selected raw materials were subjected to high-energy ball milling and pickling treatment, and the processed powders were placed in Carry out vacuum treatment at 600 °C in a high-temperature vacuum furnace with a vacuum degree of 1 Pa and a holding time of 120 minutes, then put it into a high-melting point packaging material for packaging and pre-press under a pressure of 600 MPa to obtain a cylindrical inclusion, and then put Put into the salt tube in the pyrophyllite synthesis block, the upper and lower ends of the salt tube are sealed with salt sheets to form a salt column, and then the salt column is put into the graphite tube, and the upper and lower ends of the graphite tube are assembled with graphite sheets in turn to form an ink column, and then the The graphite column is placed in the dolomite tube, and the two ends of the dolomite tube are assembled with dolomite sheet, molybdenum sheet and conductive steel ring with graphite column in the middle. Molybdenum sheet and conductive steel ring. After assembly, put the synthetic block into the synthetic chamber of the large press, press at a temperature of 1000 ℃, press about 4 GPa, hold the heat for 70 minutes, take out the material after cooling down and releasing the pressure, soak in aqua regia, and remove the metal inclusions Afterwards, a MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body is obtained.

Example 23: Taking hexagonal molybdenum disilicide and hexagonal molybdenum trisilicide pentamolybdenum powders with a mass ratio of 19:3 as initial raw materials, the selected raw materials were subjected to high-energy ball milling and pickling treatment, and the processed powders were placed in Carry out vacuum treatment at 600 °C in a high-temperature vacuum furnace with a vacuum degree of 1 Pa and a holding time of 120 minutes, then put it into a high-melting point packaging material for packaging and pre-press under a pressure of 600 MPa to obtain a cylindrical inclusion, and then put Put into the salt tube in the pyrophyllite synthesis block, the upper and lower ends of the salt tube are sealed with salt sheets to form a salt column, and then the salt column is put into the graphite tube, and the upper and lower ends of the graphite tube are assembled with graphite sheets in turn to form an ink column, and then the The graphite column is placed in the dolomite tube, and the two ends of the dolomite tube are assembled with dolomite sheet, molybdenum sheet and conductive steel ring with graphite column in the middle. Molybdenum sheet and conductive steel ring. After assembling, put the synthetic block into the synthetic chamber of the large press, press at a temperature of 900 ℃, press about 5 GPa, hold the heat for 90 minutes, take out the material after cooling down and releasing the pressure, soak in aqua regia, and remove the metal inclusions Afterwards, a MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body is obtained.

Example 24: Taking hexagonal molybdenum disilicide and hexagonal molybdenum trisilicide pentamolybdenum powders with a mass ratio of 19:31 as initial raw materials, the selected raw materials were subjected to high-energy ball milling and pickling treatment, and the processed powders were placed in Carry out vacuum treatment at 600 °C in a high-temperature vacuum furnace with a vacuum degree of 1 Pa and a holding time of 120 minutes, then put it into a high-melting point packaging material for packaging and pre-press under a pressure of 600 MPa to obtain a cylindrical inclusion, and then put Put into the salt tube in the pyrophyllite synthesis block, the upper and lower ends of the salt tube are sealed with salt sheets to form a salt column, and then the salt column is put into the graphite tube, and the upper and lower ends of the graphite tube are assembled with graphite sheets in turn to form an ink column, and then the The graphite column is placed in the dolomite tube, and the two ends of the dolomite tube are assembled with dolomite sheet, molybdenum sheet and conductive steel ring with graphite column in the middle. Molybdenum sheet and conductive steel ring. After assembly, put the synthetic block into the synthetic chamber of the large press, press at a temperature of 1100 ℃, press about 5.5 GPa, keep the heat for 20 minutes, take out the material after cooling down and releasing the pressure, soak in aqua regia, and remove the metal inclusions Afterwards, a MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body is obtained.

Embodiment 25: Take hexagonal molybdenum disilicide and hexagonal molybdenum trisilicide pentamolybdenum powders with a mass ratio of 19:3 as initial raw materials, carry out high-energy ball milling and pickling treatment on the selected raw materials, and put the processed powders into Carry out vacuum treatment at 600 °C in a high-temperature vacuum furnace with a vacuum degree of 1 Pa and a holding time of 120 minutes, then put it into a high-melting point packaging material for packaging and pre-press under a pressure of 600 MPa to obtain a cylindrical inclusion, and then put Put into the salt tube in the pyrophyllite synthesis block, the upper and lower ends of the salt tube are sealed with salt sheets to form a salt column, and then the salt column is put into the graphite tube, and the upper and lower ends of the graphite tube are assembled with graphite sheets in turn to form an ink column, and then the The graphite column is placed in the dolomite tube, and the two ends of the dolomite tube are assembled with dolomite sheet, molybdenum sheet and conductive steel ring with graphite column in the middle. Molybdenum sheet and conductive steel ring. After assembling, put the synthetic block into the synthetic chamber of the large press, press at a temperature of 1500 ℃, press about 9 GPa, hold the heat for 15 minutes, take out the material after cooling down and releasing the pressure, soak in aqua regia, and remove the metal inclusions Afterwards, a MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body is obtained.

Example 26: Taking hexagonal molybdenum disilicide and hexagonal molybdenum trisilicide pentamolybdenum powders with a mass ratio of 19:3 as initial raw materials, the selected raw materials were subjected to high-energy ball milling and pickling treatment, and the processed powders were placed in Carry out vacuum treatment at 600 °C in a high-temperature vacuum furnace with a vacuum degree of 1 Pa and a holding time of 120 minutes, then put it into a high-melting point packaging material for packaging and pre-press under a pressure of 600 MPa to obtain a cylindrical inclusion, and then put Put into the salt tube in the pyrophyllite synthesis block, the upper and lower ends of the salt tube are sealed with salt sheets to form a salt column, and then the salt column is put into the graphite tube, and the upper and lower ends of the graphite tube are assembled with graphite sheets in turn to form an ink column, and then the The graphite column is placed in the dolomite tube, and the two ends of the dolomite tube are assembled with dolomite sheet, molybdenum sheet and conductive steel ring with graphite column in the middle. Molybdenum sheet and conductive steel ring. After assembly, put the synthetic block into the synthetic chamber of the large press, press at a temperature of 1200 ℃, press about 10 GPa, hold the heat for 5 minutes, take out the material after cooling down and releasing the pressure, soak in aqua regia, and remove the metal inclusions Afterwards, a MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body is obtained.

Example 27: Taking hexagonal molybdenum disilicide and hexagonal molybdenum trisilicide pentamolybdenum powders with a mass ratio of 19:3 as initial raw materials, the selected raw materials were subjected to high-energy ball milling and pickling treatment, and the processed powders were placed in Carry out vacuum treatment at 600 °C in a high-temperature vacuum furnace with a vacuum degree of 1 Pa and a holding time of 120 minutes, then put it into a high-melting point packaging material for packaging and pre-press under a pressure of 600 MPa to obtain a cylindrical inclusion, and then put Put into the salt tube in the pyrophyllite synthesis block, the upper and lower ends of the salt tube are sealed with salt sheets to form a salt column, and then the salt column is put into the graphite tube, and the upper and lower ends of the graphite tube are assembled with graphite sheets in turn to form an ink column, and then the The graphite column is placed in the dolomite tube, and the two ends of the dolomite tube are assembled with dolomite sheet, molybdenum sheet and conductive steel ring with graphite column in the middle. Molybdenum sheet and conductive steel ring. After assembly, put the synthetic block into the synthetic chamber of the large press, press at a temperature of 1400 ℃, press about 11 GPa, keep the heat for 30 minutes, take out the material after cooling down and releasing the pressure, soak in aqua regia, and remove the metal inclusions Afterwards, a MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body is obtained.

Example 28: Taking hexagonal molybdenum disilicide and hexagonal molybdenum trisilicide pentamolybdenum powders with a mass ratio of 19:3 as initial raw materials, the selected raw materials were subjected to high-energy ball milling and pickling treatment, and the processed powders were placed in Carry out vacuum treatment at 600 °C in a high-temperature vacuum furnace with a vacuum degree of 1 Pa and a holding time of 120 minutes, then put it into a high-melting point packaging material for packaging and pre-press under a pressure of 600 MPa to obtain a cylindrical inclusion, and then put Put into the salt tube in the pyrophyllite synthesis block, the upper and lower ends of the salt tube are sealed with salt sheets to form a salt column, and then the salt column is put into the graphite tube, and the upper and lower ends of the graphite tube are assembled with graphite sheets in turn to form an ink column, and then the The graphite column is placed in the dolomite tube, and the two ends of the dolomite tube are assembled with dolomite sheet, molybdenum sheet and conductive steel ring with graphite column in the middle. Molybdenum sheet and conductive steel ring. After assembling, put the synthetic block into the synthetic cavity of the large press, press at a temperature of 1800 ℃, press about 12 GPa, hold the heat for 40 minutes, take out the material after cooling down and releasing the pressure, soak in aqua regia, and remove the metal inclusions Afterwards, a MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body is obtained.

Example 29: Taking hexagonal molybdenum disilicide and hexagonal molybdenum trisilicide pentamolybdenum powders with a mass ratio of 19:3 as initial raw materials, the selected raw materials were subjected to high-energy ball milling and pickling treatment, and the processed powders were placed in Carry out vacuum treatment at 600 °C in a high-temperature vacuum furnace with a vacuum degree of 1 Pa and a holding time of 120 minutes, then put it into a high-melting point packaging material for packaging and pre-press under a pressure of 600 MPa to obtain a cylindrical inclusion, and then put Put into the salt tube in the pyrophyllite synthesis block, the upper and lower ends of the salt tube are sealed with salt sheets to form a salt column, and then the salt column is put into the graphite tube, and the upper and lower ends of the graphite tube are assembled with graphite sheets in turn to form an ink column, and then the The graphite column is placed in the dolomite tube, and the two ends of the dolomite tube are assembled with dolomite sheet, molybdenum sheet and conductive steel ring with graphite column in the middle. Molybdenum sheet and conductive steel ring. After assembling, put the synthetic block into the synthetic cavity of the large press, press at a temperature of 1600 ℃, press about 13 GPa, keep the heat for 15 minutes, take out the material after cooling down and releasing the pressure, soak in aqua regia, and remove the metal inclusions Afterwards, a MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body is obtained.

Example 30: Take hexagonal molybdenum disilicide and hexagonal molybdenum trisilicide pentamolybdenum powders with a mass ratio of 19:3 as initial raw materials, carry out high-energy ball milling and pickling treatment on the selected raw materials, and place the processed powders in Carry out vacuum treatment at 600 ℃ in a high-temperature vacuum furnace, the vacuum degree is 1 Pa, and the holding time is 120 minutes. In the salt tube in the pyrophyllite synthesis block, the upper and lower ends of the salt tube are sealed with salt sheets to form a salt column, and then the salt column is put into the graphite tube, and the upper and lower ends of the graphite tube are sequentially assembled with graphite sheets to form an ink column, and then the graphite The column is placed in a dolomite tube, and the two ends of the dolomite tube are assembled with a dolomite sheet with a graphite column in the middle, a molybdenum sheet and a conductive steel ring. Molybdenum sheet and conductive steel ring. After assembling, put the synthetic block into the synthetic cavity of the large press, press at a temperature of 1500 ℃, press about 15 GPa, keep the heat for 5 minutes, take out the material after cooling down and releasing the pressure, soak in aqua regia, and remove the metal inclusions Afterwards, a MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body is obtained.

Example 31: Take hexagonal molybdenum disilicide and hexagonal molybdenum trisilicide pentamolybdenum powders with a mass ratio of 4:1 as initial raw materials, carry out high-energy ball milling and pickling treatment on the selected raw materials, and put the processed powders into Carry out vacuum treatment at 600 °C in a high-temperature vacuum furnace with a vacuum degree of 1 Pa and a holding time of 120 minutes, then put it into a high-melting point packaging material for packaging and pre-press under a pressure of 600 MPa to obtain a cylindrical inclusion, and then put Put into the salt tube in the pyrophyllite synthesis block, the upper and lower ends of the salt tube are sealed with salt sheets to form a salt column, and then the salt column is put into the graphite tube, and the upper and lower ends of the graphite tube are assembled with graphite sheets in turn to form an ink column, and then the The graphite column is placed in the dolomite tube, and the two ends of the dolomite tube are assembled with dolomite sheet, molybdenum sheet and conductive steel ring with graphite column in the middle. Molybdenum sheet and conductive steel ring. After assembly, put the synthetic block into the synthetic chamber of the large press, press at a temperature of 1500 ℃, press about 5GPa, keep the heat for 20 minutes, take out the material after cooling down and releasing the pressure, soak in aqua regia, and remove the metal inclusions The MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body can be easily obtained.

Example 32: Taking hexagonal molybdenum disilicide and hexagonal molybdenum trisilicide pentamolybdenum powders with a mass ratio of 4:1 as initial raw materials, the selected raw materials were subjected to high-energy ball milling and pickling treatment, and the processed powders were placed in Carry out vacuum treatment at 600 °C in a high-temperature vacuum furnace with a vacuum degree of 1 Pa and a holding time of 120 minutes, then put it into a high-melting point packaging material for packaging and pre-press under a pressure of 600 MPa to obtain a cylindrical inclusion, and then put Put into the salt tube in the pyrophyllite synthesis block, the upper and lower ends of the salt tube are sealed with salt sheets to form a salt column, and then the salt column is put into the graphite tube, and the upper and lower ends of the graphite tube are assembled with graphite sheets in turn to form an ink column, and then the The graphite column is placed in the dolomite tube, and the two ends of the dolomite tube are assembled with dolomite sheet, molybdenum sheet and conductive steel ring with graphite column in the middle. Molybdenum sheet and conductive steel ring. After assembling, put the synthetic block into the synthetic cavity of the large press, press at a temperature of 1600 °C, press about 5.5 GPa, keep the heat for 10 minutes, take out the material after cooling down and releasing the pressure, soak in aqua regia, and remove the metal inclusions Afterwards, a MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body is obtained.

Example Thirty-Three: Taking hexagonal molybdenum disilicide and hexagonal molybdenum trisilicide pentamolybdenum powders with a mass ratio of 4:1 as initial raw materials, the selected raw materials were subjected to high-energy ball milling and pickling treatment, and the processed powders were placed in Carry out vacuum treatment at 600 °C in a high-temperature vacuum furnace with a vacuum degree of 1 Pa and a holding time of 120 minutes, then put it into a high-melting point packaging material for packaging and pre-press under a pressure of 600 MPa to obtain a cylindrical inclusion, and then put Put into the salt tube in the pyrophyllite synthesis block, the upper and lower ends of the salt tube are sealed with salt sheets to form a salt column, and then the salt column is put into the graphite tube, and the upper and lower ends of the graphite tube are assembled with graphite sheets in turn to form an ink column, and then the The graphite column is placed in the dolomite tube, and the two ends of the dolomite tube are assembled with dolomite sheet, molybdenum sheet and conductive steel ring with graphite column in the middle. Molybdenum sheet and conductive steel ring. After assembly, put the synthetic block into the synthetic chamber of the large press, press at a temperature of 1700 ℃, press about 8 GPa, hold the heat for 5 minutes, take out the material after cooling down and releasing the pressure, soak in aqua regia, and remove the metal inclusions Afterwards, a MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body is obtained.

Example 34: Take hexagonal molybdenum disilicide and hexagonal molybdenum trisilicide pentamolybdenum powders with a mass ratio of 4:1 as initial raw materials, perform high-energy ball milling and pickling treatment on the selected raw materials, and put the processed powders into Carry out vacuum treatment at 600 °C in a high-temperature vacuum furnace with a vacuum degree of 1 Pa and a holding time of 120 minutes, then put it into a high-melting point packaging material for packaging and pre-press under a pressure of 600 MPa to obtain a cylindrical inclusion, and then put Put into the salt tube in the pyrophyllite synthesis block, the upper and lower ends of the salt tube are sealed with salt sheets to form a salt column, and then the salt column is put into the graphite tube, and the upper and lower ends of the graphite tube are assembled with graphite sheets in turn to form an ink column, and then the The graphite column is placed in the dolomite tube, and the two ends of the dolomite tube are assembled with dolomite sheet, molybdenum sheet and conductive steel ring with graphite column in the middle. Molybdenum sheet and conductive steel ring. After assembling, put the synthetic block into the synthetic cavity of the large press, press at a temperature of 1000 ℃, press about 9 GPa, keep the heat for 20 minutes, take out the material after cooling down and releasing the pressure, soak in aqua regia, and remove the metal inclusions Afterwards, a MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body is obtained.

Example 35: Taking hexagonal molybdenum disilicide and hexagonal molybdenum trisilicide pentamolybdenum powders with a mass ratio of 4:1 as initial raw materials, the selected raw materials were subjected to high-energy ball milling and pickling treatment, and the processed powders were placed in Carry out vacuum treatment at 600 °C in a high-temperature vacuum furnace with a vacuum degree of 1 Pa and a holding time of 120 minutes, then put it into a high-melting point packaging material for packaging and pre-press under a pressure of 600 MPa to obtain a cylindrical inclusion, and then put Put into the salt tube in the pyrophyllite synthesis block, the upper and lower ends of the salt tube are sealed with salt sheets to form a salt column, and then the salt column is put into the graphite tube, and the upper and lower ends of the graphite tube are assembled with graphite sheets in turn to form an ink column, and then the The graphite column is placed in the dolomite tube, and the two ends of the dolomite tube are assembled with dolomite sheet, molybdenum sheet and conductive steel ring with graphite column in the middle. Molybdenum sheet and conductive steel ring. After assembling, put the synthetic block into the synthetic cavity of the large press, press at a temperature of 1000 ℃, press about 10 GPa, hold the heat for 30 minutes, take out the material after cooling down and releasing the pressure, soak in aqua regia, and remove the metal inclusions Afterwards, a MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body is obtained.

Example 36: Taking hexagonal molybdenum disilicide and hexagonal molybdenum trisilicide pentamolybdenum powders with a mass ratio of 4:1 as initial raw materials, the selected raw materials were subjected to high-energy ball milling and pickling treatment, and the processed powders were placed in Carry out vacuum treatment at 600 °C in a high-temperature vacuum furnace with a vacuum degree of 1 Pa and a holding time of 120 minutes, then put it into a high-melting point packaging material for packaging and pre-press under a pressure of 600 MPa to obtain a cylindrical inclusion, and then put Put into the salt tube in the pyrophyllite synthesis block, the upper and lower ends of the salt tube are sealed with salt sheets to form a salt column, and then the salt column is put into the graphite tube, and the upper and lower ends of the graphite tube are assembled with graphite sheets in turn to form an ink column, and then the The graphite column is placed in the dolomite tube, and the two ends of the dolomite tube are assembled with dolomite sheet, molybdenum sheet and conductive steel ring with graphite column in the middle. Molybdenum sheet and conductive steel ring. After assembling, put the synthetic block into the synthetic chamber of the large press, press at about 11 GPa at a temperature of 700 ℃, keep the heat for 50 minutes, take out the material after cooling down and releasing the pressure, soak it in aqua regia, and remove the metal inclusions Afterwards, a MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body is obtained.

Example 37: Taking hexagonal molybdenum disilicide and hexagonal molybdenum trisilicide pentamolybdenum powders with a mass ratio of 4:1 as initial raw materials, the selected raw materials were subjected to high-energy ball milling and pickling treatment, and the processed powders were placed in Carry out vacuum treatment at 600 °C in a high-temperature vacuum furnace with a vacuum degree of 1 Pa and a holding time of 120 minutes, then put it into a high-melting point packaging material for packaging and pre-press under a pressure of 600 MPa to obtain a cylindrical inclusion, and then put Put into the salt tube in the pyrophyllite synthesis block, the upper and lower ends of the salt tube are sealed with salt sheets to form a salt column, and then the salt column is put into the graphite tube, and the upper and lower ends of the graphite tube are assembled with graphite sheets in turn to form an ink column, and then the The graphite column is placed in the dolomite tube, and the two ends of the dolomite tube are assembled with dolomite sheet, molybdenum sheet and conductive steel ring with graphite column in the middle. Molybdenum sheet and conductive steel ring. After assembling, put the synthetic block into the synthetic chamber of the large press, press at about 12 GPa at a temperature of 900 ℃, keep the heat for 40 minutes, take out the material after cooling down and releasing the pressure, soak in aqua regia, and remove the metal inclusions Afterwards, a MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body is obtained.

Example 38: Take hexagonal molybdenum disilicide and hexagonal molybdenum trisilicide pentamolybdenum powders with a mass ratio of 4:1 as initial raw materials, perform high-energy ball milling and pickling treatment on the selected raw materials, and put the processed powders into Carry out vacuum treatment at 600 °C in a high-temperature vacuum furnace with a vacuum degree of 1 Pa and a holding time of 120 minutes, then put it into a high-melting point packaging material for packaging and pre-press under a pressure of 600 MPa to obtain a cylindrical inclusion, and then put Put into the salt tube in the pyrophyllite synthesis block, the upper and lower ends of the salt tube are sealed with salt sheets to form a salt column, and then the salt column is put into the graphite tube, and the upper and lower ends of the graphite tube are assembled with graphite sheets in turn to form an ink column, and then the The graphite column is placed in the dolomite tube, and the two ends of the dolomite tube are assembled with dolomite sheet, molybdenum sheet and conductive steel ring with graphite column in the middle. Molybdenum sheet and conductive steel ring. After assembling, put the synthetic block into the synthetic chamber of the large press, at a temperature of 1300 ℃, press about 13 GPa, keep the heat for 70 minutes, take out the material after cooling down and releasing the pressure, soak in aqua regia, and remove the metal inclusions Afterwards, a MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body is obtained.

Example 39: Take hexagonal molybdenum disilicide and hexagonal molybdenum trisilicide pentamolybdenum powders with a mass ratio of 4:1 as initial raw materials, perform high-energy ball milling and pickling treatment on the selected raw materials, and put the processed powders into Carry out vacuum treatment at 600 °C in a high-temperature vacuum furnace with a vacuum degree of 1 Pa and a holding time of 120 minutes, then put it into a high-melting point packaging material for packaging and pre-press under a pressure of 600 MPa to obtain a cylindrical inclusion, and then put Put into the salt tube in the pyrophyllite synthesis block, the upper and lower ends of the salt tube are sealed with salt sheets to form a salt column, and then the salt column is put into the graphite tube, and the upper and lower ends of the graphite tube are assembled with graphite sheets in turn to form an ink column, and then the The graphite column is placed in the dolomite tube, and the two ends of the dolomite tube are assembled with dolomite sheet, molybdenum sheet and conductive steel ring with graphite column in the middle. Molybdenum sheet and conductive steel ring. After assembly, put the synthetic block into the synthetic chamber of the large press, press at a temperature of 1400 ℃, press about 14 GPa, keep the heat for 60 minutes, take out the material after cooling down and releasing the pressure, soak in aqua regia, and remove the metal inclusions Afterwards, a MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body is obtained.

Example 40: Taking hexagonal molybdenum disilicide and hexagonal molybdenum trisilicide pentamolybdenum powders with a mass ratio of 4:1 as initial raw materials, the selected raw materials were subjected to high-energy ball milling and pickling treatment, and the processed powders were placed in Carry out vacuum treatment at 600 ℃ in a high-temperature vacuum furnace, the vacuum degree is 1 Pa, and the holding time is 120 minutes. In the salt tube in the pyrophyllite synthesis block, the upper and lower ends of the salt tube are sealed with salt sheets to form a salt column, and then the salt column is put into the graphite tube, and the upper and lower ends of the graphite tube are sequentially assembled with graphite sheets to form an ink column, and then the graphite The column is placed in a dolomite tube, and the two ends of the dolomite tube are assembled with a dolomite sheet with a graphite column in the middle, a molybdenum sheet and a conductive steel ring. Molybdenum sheet and conductive steel ring. After assembling, put the synthetic block into the synthetic chamber of the large press, press at a temperature of 900 ℃, press about 15 GPa, hold the heat for 100 minutes, take out the material after cooling down and releasing the pressure, soak in aqua regia, and remove the metal inclusions Afterwards, a MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body is obtained.

Example 41: Taking hexagonal molybdenum disilicide and hexagonal molybdenum trisilicide pentamolybdenum powders with a mass ratio of 3:1 as initial raw materials, the selected raw materials were subjected to high-energy ball milling and pickling treatment, and the processed powders were placed in Carry out vacuum treatment at 600 °C in a high-temperature vacuum furnace with a vacuum degree of 1 Pa and a holding time of 120 minutes, then put it into a high-melting point packaging material for packaging and pre-press under a pressure of 600 MPa to obtain a cylindrical inclusion, and then put Put into the salt tube in the pyrophyllite synthesis block, the upper and lower ends of the salt tube are sealed with salt sheets to form a salt column, and then the salt column is put into the graphite tube, and the upper and lower ends of the graphite tube are assembled with graphite sheets in turn to form an ink column, and then the The graphite column is placed in the dolomite tube, and the two ends of the dolomite tube are assembled with dolomite sheet, molybdenum sheet and conductive steel ring with graphite column in the middle. Molybdenum sheet and conductive steel ring. After assembly, put the synthetic block into the synthetic chamber of the large press, press at a temperature of 800 ℃, press about 4 GPa, keep the heat for 60 minutes, take out the material after cooling down and releasing the pressure, soak in aqua regia, and remove the metal inclusions Afterwards, a MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body is obtained.

Example 42: Taking hexagonal molybdenum disilicide and hexagonal molybdenum trisilicide pentamolybdenum powders with a mass ratio of 3:1 as initial raw materials, the selected raw materials were subjected to high-energy ball milling and pickling treatment, and the processed powders were placed in Carry out vacuum treatment at 600 °C in a high-temperature vacuum furnace with a vacuum degree of 1 Pa and a holding time of 120 minutes, then put it into a high-melting point packaging material for packaging and pre-press under a pressure of 600 MPa to obtain a cylindrical inclusion, and then put Put into the salt tube in the pyrophyllite synthesis block, the upper and lower ends of the salt tube are sealed with salt sheets to form a salt column, and then the salt column is put into the graphite tube, and the upper and lower ends of the graphite tube are assembled with graphite sheets in turn to form an ink column, and then the The graphite column is placed in the dolomite tube, and the two ends of the dolomite tube are assembled with dolomite sheet, molybdenum sheet and conductive steel ring with graphite column in the middle. Molybdenum sheet and conductive steel ring. After assembly, put the synthetic block into the synthetic chamber of the large press, press at a temperature of 1000 ℃, press about 5.5 GPa, keep the heat for 20 minutes, take out the material after cooling down and releasing the pressure, soak in aqua regia, and remove the metal inclusions Afterwards, a MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body is obtained.

Example 43: Taking hexagonal molybdenum disilicide and hexagonal molybdenum trisilicide pentamolybdenum powders with a mass ratio of 3:1 as initial raw materials, the selected raw materials were subjected to high-energy ball milling and pickling treatment, and the processed powders were placed in Carry out vacuum treatment at 600 °C in a high-temperature vacuum furnace with a vacuum degree of 1 Pa and a holding time of 120 minutes, then put it into a high-melting point packaging material for packaging and pre-press under a pressure of 600 MPa to obtain a cylindrical inclusion, and then put Put into the salt tube in the pyrophyllite synthesis block, the upper and lower ends of the salt tube are sealed with salt sheets to form a salt column, and then the salt column is put into the graphite tube, and the upper and lower ends of the graphite tube are assembled with graphite sheets in turn to form an ink column, and then the The graphite column is placed in the dolomite tube, and the two ends of the dolomite tube are assembled with dolomite sheet, molybdenum sheet and conductive steel ring with graphite column in the middle. Molybdenum sheet and conductive steel ring. After assembling, put the synthetic block into the synthetic chamber of the large press, press at a temperature of 1200 ℃, press about 6 GPa, keep the heat for 70 minutes, take out the material after cooling down and releasing the pressure, soak in aqua regia, and remove the metal inclusions Afterwards, a MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body is obtained.

Example 44: Taking hexagonal molybdenum disilicide and hexagonal molybdenum trisilicide pentamolybdenum powders with a mass ratio of 3:1 as initial raw materials, the selected raw materials were subjected to high-energy ball milling and pickling treatment, and the processed powders were placed in Carry out vacuum treatment at 600 °C in a high-temperature vacuum furnace with a vacuum degree of 1 Pa and a holding time of 120 minutes, then put it into a high-melting point packaging material for packaging and pre-press under a pressure of 600 MPa to obtain a cylindrical inclusion, and then put Put into the salt tube in the pyrophyllite synthesis block, the upper and lower ends of the salt tube are sealed with salt sheets to form a salt column, and then the salt column is put into the graphite tube, and the upper and lower ends of the graphite tube are assembled with graphite sheets in turn to form an ink column, and then the The graphite column is placed in the dolomite tube, and the two ends of the dolomite tube are assembled with dolomite sheet, molybdenum sheet and conductive steel ring with graphite column in the middle. Molybdenum sheet and conductive steel ring. After assembling, put the synthetic block into the synthetic chamber of the large press, press at about 7 GPa at a temperature of 110 ℃, keep the heat for 10 minutes, take out the material after cooling down and releasing the pressure, soak in aqua regia, and remove the metal inclusions Afterwards, a MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body is obtained.

Example 45: Taking hexagonal molybdenum disilicide and hexagonal molybdenum trisilicide pentamolybdenum powders with a mass ratio of 3:1 as initial raw materials, the selected raw materials were subjected to high-energy ball milling and pickling treatment, and the processed powders were placed in Carry out vacuum treatment at 600 °C in a high-temperature vacuum furnace with a vacuum degree of 1 Pa and a holding time of 120 minutes, then put it into a high-melting point packaging material for packaging and pre-press under a pressure of 600 MPa to obtain a cylindrical inclusion, and then put Put into the salt tube in the pyrophyllite synthesis block, the upper and lower ends of the salt tube are sealed with salt sheets to form a salt column, and then the salt column is put into the graphite tube, and the upper and lower ends of the graphite tube are assembled with graphite sheets in turn to form an ink column, and then the The graphite column is placed in the dolomite tube, and the two ends of the dolomite tube are assembled with dolomite sheet, molybdenum sheet and conductive steel ring with graphite column in the middle. Molybdenum sheet and conductive steel ring. After assembly, put the synthetic block into the synthetic chamber of the large press, press at a temperature of 900 ℃, press about 8 GPa, hold the heat for 100 minutes, take out the material after cooling down and releasing the pressure, soak in aqua regia, and remove the metal inclusions Afterwards, a MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body is obtained.

Example 46: Taking hexagonal molybdenum disilicide and hexagonal molybdenum trisilicide pentamolybdenum powders with a mass ratio of 3:1 as initial raw materials, the selected raw materials were subjected to high-energy ball milling and pickling treatment, and the processed powders were placed in Carry out vacuum treatment at 600 °C in a high-temperature vacuum furnace with a vacuum degree of 1 Pa and a holding time of 120 minutes, then put it into a high-melting point packaging material for packaging and pre-press under a pressure of 600 MPa to obtain a cylindrical inclusion, and then put Put into the salt tube in the pyrophyllite synthesis block, the upper and lower ends of the salt tube are sealed with salt sheets to form a salt column, and then the salt column is put into the graphite tube, and the upper and lower ends of the graphite tube are assembled with graphite sheets in turn to form an ink column, and then the The graphite column is placed in the dolomite tube, and the two ends of the dolomite tube are assembled with dolomite sheet, molybdenum sheet and conductive steel ring with graphite column in the middle. Molybdenum sheet and conductive steel ring. After assembly, put the synthetic block into the synthetic chamber of the large press, press at a temperature of 1300 ℃, press about 9 GPa, hold the heat for 5 minutes, take out the material after cooling down and releasing the pressure, soak in aqua regia, and remove the metal inclusions Afterwards, a MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body is obtained.

Example 47: Taking hexagonal molybdenum disilicide and hexagonal molybdenum trisilicide pentamolybdenum powders with a mass ratio of 3:1 as initial raw materials, the selected raw materials were subjected to high-energy ball milling and pickling treatment, and the processed powders were placed in Carry out vacuum treatment at 600 °C in a high-temperature vacuum furnace with a vacuum degree of 1 Pa and a holding time of 120 minutes, then put it into a high-melting point packaging material for packaging and pre-press under a pressure of 600 MPa to obtain a cylindrical inclusion, and then put Put into the salt tube in the pyrophyllite synthesis block, the upper and lower ends of the salt tube are sealed with salt sheets to form a salt column, and then the salt column is put into the graphite tube, and the upper and lower ends of the graphite tube are assembled with graphite sheets in turn to form an ink column, and then the The graphite column is placed in the dolomite tube, and the two ends of the dolomite tube are assembled with dolomite sheet, molybdenum sheet and conductive steel ring with graphite column in the middle. Molybdenum sheet and conductive steel ring. After assembling, put the synthetic block into the synthetic chamber of the large press, press at a temperature of 1500 ℃, press about 10 GPa, hold the heat for 30 minutes, take out the material after cooling down and releasing the pressure, soak in aqua regia, and remove the metal inclusions Afterwards, a MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body is obtained.

Example 48: Taking hexagonal molybdenum disilicide and hexagonal molybdenum trisilicide pentamolybdenum powders with a mass ratio of 19:1 as initial raw materials, the selected raw materials were subjected to high-energy ball milling and pickling treatment, and the processed powders were placed at high temperature Carry out vacuum treatment at 600 °C in a vacuum furnace with a vacuum degree of 1 Pa and a holding time of 120 minutes, then put it into a high-melting point wrapping material for packaging and pre-press under a pressure of 600 MPa to obtain a cylindrical inclusion, and then put pyrophyllite In the salt tube in the synthesis block, the upper and lower ends of the salt tube are sealed with salt sheets to form a salt column, and then the salt column is put into the graphite tube, and the upper and lower ends of the graphite tube are assembled with graphite sheets in turn to form an ink column, and then the graphite column Placed in a dolomite tube, the two ends of the dolomite tube are assembled with a dolomite sheet with a graphite column in the middle, a molybdenum sheet and a conductive steel ring. Molybdenum sheet and conductive steel ring. After assembling, put the synthetic block into the synthetic chamber of the large press, press at a temperature of 1600 ℃, press about 11 GPa, hold the heat for 20 minutes, take out the material after cooling down and releasing the pressure, soak in aqua regia, and remove the metal inclusions Afterwards, a MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body is obtained.

Example 49: Taking hexagonal molybdenum disilicide and hexagonal molybdenum trisilicide pentamolybdenum powders with a mass ratio of 3:1 as initial raw materials, the selected raw materials were subjected to high-energy ball milling and pickling treatment, and the processed powders were placed in Carry out vacuum treatment at 600 °C in a high-temperature vacuum furnace with a vacuum degree of 1 Pa and a holding time of 120 minutes, then put it into a high-melting point packaging material for packaging and pre-press under a pressure of 600 MPa to obtain a cylindrical inclusion, and then put Put into the salt tube in the pyrophyllite synthesis block, the upper and lower ends of the salt tube are sealed with salt sheets to form a salt column, and then the salt column is put into the graphite tube, and the upper and lower ends of the graphite tube are assembled with graphite sheets in turn to form an ink column, and then the The graphite column is placed in the dolomite tube, and the two ends of the dolomite tube are assembled with dolomite sheet, molybdenum sheet and conductive steel ring with graphite column in the middle. Molybdenum sheet and conductive steel ring. After assembly, put the synthetic block into the synthetic chamber of the large press, press at a temperature of 1200 ℃, press about 13 GPa, keep the heat for 10 minutes, take out the material after cooling down and releasing the pressure, soak in aqua regia, and remove the metal inclusions Afterwards, a MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body is obtained.

Example 50: Take hexagonal molybdenum disilicide and hexagonal molybdenum trisilicide pentamolybdenum powders with a mass ratio of 3:1 as initial raw materials, carry out high-energy ball milling and pickling treatment on the selected raw materials, and place the processed powders in Carry out vacuum treatment at 600 ℃ in a high-temperature vacuum furnace, the vacuum degree is 1 Pa, and the holding time is 120 minutes. In the salt tube in the pyrophyllite synthesis block, the upper and lower ends of the salt tube are sealed with salt sheets to form a salt column, and then the salt column is put into the graphite tube, and the upper and lower ends of the graphite tube are sequentially assembled with graphite sheets to form an ink column, and then the graphite The column is placed in a dolomite tube, and the two ends of the dolomite tube are assembled with a dolomite sheet with a graphite column in the middle, a molybdenum sheet and a conductive steel ring. Molybdenum sheet and conductive steel ring. After assembly, put the synthetic block into the synthetic chamber of the large press, press at a temperature of 1400 ℃, press about 15 GPa, hold the heat for 40 minutes, take out the material after cooling down and releasing the pressure, soak in aqua regia, and remove the metal inclusions Afterwards, a MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body is obtained.

Example 51: Taking hexagonal molybdenum disilicide and hexagonal molybdenum trisilicide pentamolybdenum powders with a mass ratio of 7:3 as initial raw materials, the selected raw materials were subjected to high-energy ball milling and pickling treatment, and the processed powders were placed in Carry out vacuum treatment at 600 °C in a high-temperature vacuum furnace with a vacuum degree of 1 Pa and a holding time of 120 minutes, then put it into a high-melting point packaging material for packaging and pre-press under a pressure of 600 MPa to obtain a cylindrical inclusion, and then put Put into the salt tube in the pyrophyllite synthesis block, the upper and lower ends of the salt tube are sealed with salt sheets to form a salt column, and then the salt column is put into the graphite tube, and the upper and lower ends of the graphite tube are assembled with graphite sheets in turn to form an ink column, and then the The graphite column is placed in the dolomite tube, and the two ends of the dolomite tube are assembled with dolomite sheet, molybdenum sheet and conductive steel ring with graphite column in the middle. Molybdenum sheet and conductive steel ring. After assembly, put the synthetic block into the synthetic chamber of the large press, press at a temperature of 1000 ℃, press about 5.5 GPa, keep the heat for 20 minutes, take out the material after cooling down and releasing the pressure, soak in aqua regia, and remove the metal inclusions Afterwards, a MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body is obtained.

Example 52: Taking hexagonal molybdenum disilicide and hexagonal molybdenum trisilicide pentamolybdenum powders with a mass ratio of 7:3 as initial raw materials, the selected raw materials were subjected to high-energy ball milling and pickling treatment, and the processed powders were placed in Carry out vacuum treatment at 600 °C in a high-temperature vacuum furnace with a vacuum degree of 1 Pa and a holding time of 120 minutes, then put it into a high-melting point packaging material for packaging and pre-press under a pressure of 600 MPa to obtain a cylindrical inclusion, and then put Put into the salt tube in the pyrophyllite synthesis block, the upper and lower ends of the salt tube are sealed with salt sheets to form a salt column, and then the salt column is put into the graphite tube, and the upper and lower ends of the graphite tube are assembled with graphite sheets in turn to form an ink column, and then the The graphite column is placed in the dolomite tube, and the two ends of the dolomite tube are assembled with dolomite sheet, molybdenum sheet and conductive steel ring with graphite column in the middle. Molybdenum sheet and conductive steel ring. After assembling, put the synthetic block into the synthetic chamber of the large press, press at a temperature of 1200 ℃, press about 6 GPa, hold the heat for 10 minutes, take out the material after cooling down and releasing the pressure, soak in aqua regia, and remove the metal inclusions Afterwards, a MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body is obtained.

Example 53: Taking hexagonal molybdenum disilicide and hexagonal molybdenum trisilicide pentamolybdenum powders with a mass ratio of 7:3 as initial raw materials, the selected raw materials were subjected to high-energy ball milling and pickling treatment, and the processed powders were placed in Carry out vacuum treatment at 600 °C in a high-temperature vacuum furnace with a vacuum degree of 1 Pa and a holding time of 120 minutes, then put it into a high-melting point packaging material for packaging and pre-press under a pressure of 600 MPa to obtain a cylindrical inclusion, and then put Put into the salt tube in the pyrophyllite synthesis block, the upper and lower ends of the salt tube are sealed with salt sheets to form a salt column, and then the salt column is put into the graphite tube, and the upper and lower ends of the graphite tube are assembled with graphite sheets in turn to form an ink column, and then the The graphite column is placed in the dolomite tube, and the two ends of the dolomite tube are assembled with dolomite sheet, molybdenum sheet and conductive steel ring with graphite column in the middle. Molybdenum sheet and conductive steel ring. After assembling, put the synthetic block into the synthetic cavity of the large press, press at a temperature of 1100 ℃, press about 7 GPa, keep the heat for 30 minutes, take out the material after cooling down and releasing the pressure, soak in aqua regia, and remove the metal inclusions Afterwards, a MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body is obtained.

Example 54: Taking hexagonal molybdenum disilicide and hexagonal molybdenum trisilicide pentamolybdenum powders with a mass ratio of 7:3 as initial raw materials, the selected raw materials were subjected to high-energy ball milling and pickling treatment, and the processed powders were placed in Carry out vacuum treatment at 600 °C in a high-temperature vacuum furnace with a vacuum degree of 1 Pa and a holding time of 120 minutes, then put it into a high-melting point packaging material for packaging and pre-press under a pressure of 600 MPa to obtain a cylindrical inclusion, and then put Put into the salt tube in the pyrophyllite synthesis block, the upper and lower ends of the salt tube are sealed with salt sheets to form a salt column, and then the salt column is put into the graphite tube, and the upper and lower ends of the graphite tube are assembled with graphite sheets in turn to form an ink column, and then the The graphite column is placed in the dolomite tube, and the two ends of the dolomite tube are assembled with dolomite sheet, molybdenum sheet and conductive steel ring with graphite column in the middle. Molybdenum sheet and conductive steel ring. Put the synthetic block into the synthetic cavity of the large press after assembling, press at a temperature of 900 ℃, press about 8 GPa, hold the heat for 90 minutes, take out the material after cooling down and releasing the pressure, soak in aqua regia, and remove the metal inclusions Afterwards, a MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body is obtained.

Example 55: Taking hexagonal molybdenum disilicide and hexagonal molybdenum trisilicide pentamolybdenum powders with a mass ratio of 7:3 as initial raw materials, the selected raw materials were subjected to high-energy ball milling and pickling treatment, and the processed powders were placed in Carry out vacuum treatment at 600 °C in a high-temperature vacuum furnace with a vacuum degree of 1 Pa and a holding time of 120 minutes, then put it into a high-melting point packaging material for packaging and pre-press under a pressure of 600 MPa to obtain a cylindrical inclusion, and then put Put into the salt tube in the pyrophyllite synthesis block, the upper and lower ends of the salt tube are sealed with salt sheets to form a salt column, and then the salt column is put into the graphite tube, and the upper and lower ends of the graphite tube are assembled with graphite sheets in turn to form an ink column, and then the The graphite column is placed in the dolomite tube, and the two ends of the dolomite tube are assembled with dolomite sheet, molybdenum sheet and conductive steel ring with graphite column in the middle. Molybdenum sheet and conductive steel ring. After assembly, put the synthetic block into the synthetic chamber of the large press, press at a temperature of 800 ℃, press about 9 GPa, hold the heat for 80 minutes, take out the material after cooling down and releasing the pressure, soak in aqua regia, and remove the metal inclusions Afterwards, a MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body is obtained.

Example 56: Taking hexagonal molybdenum disilicide and hexagonal molybdenum trisilicide pentamolybdenum powders with a mass ratio of 7:3 as initial raw materials, the selected raw materials were subjected to high-energy ball milling and pickling treatment, and the processed powders were placed in Carry out vacuum treatment at 600 °C in a high-temperature vacuum furnace with a vacuum degree of 1 Pa and a holding time of 120 minutes, then put it into a high-melting point packaging material for packaging and pre-press under a pressure of 600 MPa to obtain a cylindrical inclusion, and then put Put into the salt tube in the pyrophyllite synthesis block, the upper and lower ends of the salt tube are sealed with salt sheets to form a salt column, and then the salt column is put into the graphite tube, and the upper and lower ends of the graphite tube are assembled with graphite sheets in turn to form an ink column, and then the The graphite column is placed in the dolomite tube, and the two ends of the dolomite tube are assembled with dolomite sheet, molybdenum sheet and conductive steel ring with graphite column in the middle. Molybdenum sheet and conductive steel ring. After assembly, put the synthetic block into the synthetic chamber of the large press, press at a temperature of 1400 ℃, press about 10 GPa, hold the heat for 40 minutes, take out the material after cooling down and releasing the pressure, soak in aqua regia, and remove the metal inclusions Afterwards, a MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body is obtained.

Example 57: Taking hexagonal molybdenum disilicide and hexagonal molybdenum trisilicide pentamolybdenum powders with a mass ratio of 7:3 as initial raw materials, the selected raw materials were subjected to high-energy ball milling and pickling treatment, and the processed powders were placed in Carry out vacuum treatment at 600 °C in a high-temperature vacuum furnace with a vacuum degree of 1 Pa and a holding time of 120 minutes, then put it into a high-melting point packaging material for packaging and pre-press under a pressure of 600 MPa to obtain a cylindrical inclusion, and then put Put into the salt tube in the pyrophyllite synthesis block, the upper and lower ends of the salt tube are sealed with salt sheets to form a salt column, and then the salt column is put into the graphite tube, and the upper and lower ends of the graphite tube are assembled with graphite sheets in turn to form an ink column, and then the The graphite column is placed in the dolomite tube, and the two ends of the dolomite tube are assembled with dolomite sheet, molybdenum sheet and conductive steel ring with graphite column in the middle. Molybdenum sheet and conductive steel ring. After assembling, put the synthetic block into the synthetic cavity of the large press, press at a temperature of 1800 ℃, press about 11 GPa, hold the heat for 20 minutes, take out the material after cooling down and releasing the pressure, soak in aqua regia, and remove the metal inclusions Afterwards, a MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body is obtained.

Example 58: Taking hexagonal molybdenum disilicide and hexagonal molybdenum trisilicide pentamolybdenum powders with a mass ratio of 7:3 as initial raw materials, the selected raw materials were subjected to high-energy ball milling and pickling treatment, and the processed powders were placed in Carry out vacuum treatment at 600 °C in a high-temperature vacuum furnace with a vacuum degree of 1 Pa and a holding time of 120 minutes, then put it into a high-melting point packaging material for packaging and pre-press under a pressure of 600 MPa to obtain a cylindrical inclusion, and then put Put into the salt tube in the pyrophyllite synthesis block, the upper and lower ends of the salt tube are sealed with salt sheets to form a salt column, and then the salt column is put into the graphite tube, and the upper and lower ends of the graphite tube are assembled with graphite sheets in turn to form an ink column, and then the The graphite column is placed in the dolomite tube, and the two ends of the dolomite tube are assembled with dolomite sheet, molybdenum sheet and conductive steel ring with graphite column in the middle. Molybdenum sheet and conductive steel ring. After assembling, put the synthetic block into the synthetic cavity of the large press, press at about 12 GPa at a temperature of 1600 ℃, keep the heat for 50 minutes, take out the material after cooling down and releasing the pressure, soak in aqua regia, and remove the metal inclusions Afterwards, a MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body is obtained.

Example 59: Taking hexagonal molybdenum disilicide and hexagonal molybdenum trisilicide pentamolybdenum powders with a mass ratio of 7:3 as initial raw materials, the selected raw materials were subjected to high-energy ball milling and pickling treatment, and the processed powders were placed in Carry out vacuum treatment at 600 °C in a high-temperature vacuum furnace with a vacuum degree of 1 Pa and a holding time of 120 minutes, then put it into a high-melting point packaging material for packaging and pre-press under a pressure of 600 MPa to obtain a cylindrical inclusion, and then put Put into the salt tube in the pyrophyllite synthesis block, the upper and lower ends of the salt tube are sealed with salt sheets to form a salt column, and then the salt column is put into the graphite tube, and the upper and lower ends of the graphite tube are assembled with graphite sheets in turn to form an ink column, and then the The graphite column is placed in the dolomite tube, and the two ends of the dolomite tube are assembled with dolomite sheet, molybdenum sheet and conductive steel ring with graphite column in the middle. Molybdenum sheet and conductive steel ring. After assembling, put the synthetic block into the synthetic cavity of the large press, press at a temperature of 1300 ℃, press about 14 GPa, hold the heat for 40 minutes, take out the material after cooling down and releasing the pressure, soak in aqua regia, and remove the metal inclusions Afterwards, a MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body is obtained.

Embodiment 60: Take hexagonal molybdenum disilicide and hexagonal molybdenum trisilicide pentamolybdenum powders with a mass ratio of 7:3 as initial raw materials, carry out high-energy ball milling and pickling treatment on the selected raw materials, and place the processed powders in Carry out vacuum treatment at 600 ℃ in a high-temperature vacuum furnace, the vacuum degree is 1 Pa, and the holding time is 120 minutes. In the salt tube in the pyrophyllite synthesis block, the upper and lower ends of the salt tube are sealed with salt sheets to form a salt column, and then the salt column is put into the graphite tube, and the upper and lower ends of the graphite tube are sequentially assembled with graphite sheets to form an ink column, and then the graphite The column is placed in a dolomite tube, and the two ends of the dolomite tube are assembled with a dolomite sheet with a graphite column in the middle, a molybdenum sheet and a conductive steel ring. Molybdenum sheet and conductive steel ring. After assembly, put the synthetic block into the synthetic chamber of the large press, press at a temperature of 1500 ℃, press about 15 GPa, keep the heat for 20 minutes, take out the material after cooling down and releasing the pressure, soak in aqua regia, and remove the metal inclusions Afterwards, a MoSi ₂ -Mo ₅ Si ₃ composite ceramic sintered body is obtained.

The above description is only a preferred embodiment of the present invention, used to illustrate the technical solutions of the present invention, and is not intended to limit the present invention. Those in the relevant technical field can also do it without departing from the spirit and scope of the present invention. Various changes, substitutions and modifications have been made, so equivalent technical solutions also belong to the category of the present invention.

Claims (9)

1. a kind of high tenacity high-temperature structural material MoSi₂-Mo₅Si₃The preparation of composite ceramics, it is characterised in that: the MoSi of preparation₂- Mo₅Si₃Composite ceramics have high tenacity, high-compactness and higher hardness and excellent inoxidizability.

2. high tenacity high-temperature structural material MoSi according to claim 1₂-Mo₅Si₃The preparation method of composite ceramics, it is special Sign is: mainly including the following steps:

(1) three silication, five molybdenum of the molybdenum disilicide for the hexagonal structure chosen and hexagonal structure is initial raw materials；

(2) raw material mixed in above-mentioned (1) are subjected to high-energy ball milling, then carry out pickling；

(3) by after pickling in above-mentioned (2) powder metallurgy be vacuum-treated, after be put into high-melting-point lapping encapsulate and be pressed into advance Cylindrical body；

(4) cylindrical body being pressed into advance in above-mentioned (3) is put into high-pressure synthesis assembly；

(5) assembled high-pressure synthesis assembly is placed in synthesis chamber and carries out high temperature and pressure sintering, sintering condition is 3 ~ 15 GPa, 700 ~ 1800 DEG C, soaking time 5 ~ 100 minutes；

(6) cool down pressure release after sintering is completed, and takes out agglomerate, and then pickling removes inclusion enclave, and claim 1 institute can be obtained The high tenacity high-temperature structural material MoSi stated₂-Mo₅Si₃Composite ceramics block sintered body.

3. high tenacity high-temperature structural material MoSi according to claim 1₂-Mo₅Si₃Composite ceramics, it is characterised in that: described Prepare MoSi₂- Mo₅Si₃Composite ceramics sintered body initial feed is the molybdenum disilicide (MoSi of hexagonal structure₂) and hexagonal structure Three silication, five molybdenum (Mo₅Si₃), form position powder or particle etc..

4. high tenacity high-temperature structural material MoSi according to claim 1₂-Mo₅Si₃Composite ceramics, it is characterised in that: the MoSi₂- Mo₅Si₃The preparation of composite ceramics uses high temperature and pressure sintering process.

5. high tenacity high-temperature structural material MoSi according to claim 3₂-Mo₅Si₃The preparation method of composite ceramics: described (1) three silication, five molybdenum of the molybdenum disilicide of hexagonal structure and hexagonal structure is mixed according to mass ratio 19:1 ~ 7:3 in.

6. high tenacity high-temperature structural material MoSi according to claim 3₂-Mo₅Si₃The preparation method of composite ceramics, it is special Sign is: for high-energy ball milling with n-hexane, ethyl alcohol or stearic acid etc. are used as mechanical milling process controlling agent in (2), with high speed steel ball, As high energy ball, the ratio of grinding media to material in Process During High Energy Ball Milling is 10:1,9:1 or 8:1, the ball for zirconia balls or agate ball Mill rate is 250 ~ 500 r/min, and Ball-milling Time is 5 ~ 50 hours.

7. high tenacity high-temperature structural material MoSi according to claim 3₂-Mo₅Si₃The preparation method of composite ceramics, it is special Sign is: the condition that (3) high temperature is vacuum-treated are as follows: 500 ~ 1500 DEG C of temperature, vacuum degree 1Pa ~ 1 × 10^-5 Pa、 Heat preservation 10 ~ 120 minutes；The pressure of precompressed cylindrical body is 200 ~ 800 MPa.

8. high tenacity high-temperature structural material MoSi according to claim 3₂-Mo₅Si₃The preparation method of composite ceramics, it is special Sign is: press is cubic hinge press, belt type press, four sides high pressure apparatus and its can generate high temperature and pressure item in (5) The equipment of part.

9. high tenacity high-temperature structural material MoSi according to claim 3₂-Mo₅Si₃The preparation method of composite ceramics, it is special Sign is: the acid in (6) is chloroazotic acid, concentrated hydrochloric acid or the concentrated sulfuric acid.